Asphaltic products and process of making the same



L. KIRSCHBRAUN. ASPHALTIC PRODUCTS AND PROCESS or MAKING THE SAME.

Patented Aug. 15, 1916.

APPLICATION FILED MAR. 29. 1912.

' heretofore 'made from petroleum residuum LESTER KIRSCHBRAUN, OF CHICAGO, ILLINOIS.

ASPHALTIG PRODUCTS AND PROCESS OF MAKING THE SAME.

Specification of Letters Patent.

Patented Aug. 15, 1916,

Application filed March 29, 1912. Serial No. 687,021.

To all whom it may concern:

Be it known that I, LESTER KIRsoHBRAUN, a citizen of the United States, residing in the city of Chicago, county of- Cook, and

State of Illinois, have invented certain new and useful Improvements in Asphaltic Products and Processes of Making the Same, of which the following is a specification.

This invention relates to improvements in asphaltic products and processes of making the same and refers more particularly to making new and improved asphaltic products from semi-'asphaltic base petroleum residuum, 1i. 6., the heavy residues left after removing the naphthas, burning oils and portions of'the lubricating oils, until the residuum referred to has a gravity of about 12 to about 24 degrees Baum.

Among the salient objects of the invention are to so treat petroleum residuum of the character referred to as to remove from such residuum the greater part of the Vaseline, parafiin and analogous hydrocarbons contained therein and without any material decomposition; to provide a process which will convert the residuum of the character in question into a new asphaltic product which will hate a remarkable degree ofductility and cementitiousness as well as other characteristics not found in asphaltic products of the character in question; to provide a process for producing products of the above mentioned character in which semi-asphaltic base petroleum residuum. is subjected to the combined action of heat and superheated steam in a still at temperatures below the boiling temperature of the residuum whereby the aforesaid hydrocarbons are 'removed at comparatively low temperatures, 71. e., below the temperatures of ordinary fractional distillation; to provide a process in which the vapor pressure of the paraffin or Vaseline hydrocarbons is in effect, so raised that these hydrocarbons will be removed from the residuum at temperatures sufliciently low to. obviate any danger of decomposition or otherwise injuring the asphaltic hydrocarbons,

the residuum by such treatment being so modified as to producea new asphaltic product; to provide a process in which the paraflin, Vaseline and other analogous hydrocarbons are removed from the residuum without being decomposed or cracked, thus avoiding the addition of deleterious substances in the resultant product; tov provide a process which is simple and economically operated and necessitates only the use of heat and'superheated steam; and in general to provide a new and improved product of the character referred to.

The invention consists in the matters hereinafter' described and more particularly pointed out in the appended claims.

In present commercial practice crude petroleum is fractionally distilled by the use of saturated steam and heat. I amaware that various writers on the distillation of crude petroleum have discussed the use of air, superheated steam and inert gases. I am also aware that artificial asphalts and asphaltic fluxes have been made from petroleum residuum or tar by subjecting heated residuum to the action of air, sulfur or saturated steam. In some cases, as for example, when air is used, the residuum has been-heated to such a degree as to cause material distillation, the air causing certain chemical reactions resulting in. cracking and the production of a solid residue. In

other cases whereair has been used the tem-- treatment of crude petroleum nor does it have anythingto do with the production of asphaltic products or asphaltic fluxes of the character last referred to. Products produced by the use of air or sulfur are not in any sense analogous or equivalent to products produced by my process. The former contain the greater proportion of the paraflin and Vaseline and analogous hydrocarbons contained in the original residuum or else contain their cracked or decomposed residues. By my process such hydrocarbons are removed without cracking or decomposition. These prior art products are relatively non-ductile, have excessively high melting points with reference to their consistency, are more or less greasy and cheesy in character, and if subjected to too high a degree of heat when being made are crumbly, brittle and non-homogeneous. The air blown asphalts for example, exhibit as one of their'main characteristics a great inert-- ness as to changes in their consistency under extremes of temperature, and are extremely viscous in character when melted. The present process produces a product which has characteristics opposite from those mentioned'in the foregoing sentence; my products having an unusual degree of ductility, in many cases having an elongation of morethan one hundred times their cross section at normal temperature, 2'. (2., 77 F. and having a high degree of adhesiveness and cementitiousness not found in asphaltic products heretofore made from semi-asphaltic base petroleum residuum. I

As stated, the present invention 1s d rected primarily to a process of treating semi-asphaltic base residuum so as to remove the greater part of the vaseline, parafl in and analogous hydrocarbons contamed 1n the residuum and in such a way as to provide a new asphaltic product. semi-asphaltlc base. residuums are obtained from the mid-con- I 'tinent and Gulf fields and more particularly I Oklahoma and Wyoming and also the Mexi-.

1' be other i from the Illinois,.Kansas, Texas, Louisiana,

can fields, although there may fields from which semi-asphaltlc base' 011s I "may be obtained. By semi-asphaltic base residuum is meant such petroleum residuum I as contains a substantial percentage of asphaltic hydrocarbons in'addition to parallin and analogous saturated hydrocarbons which are present 'in petroleum. While asphaltic products have heretofore been made from both asphaltic and semi-asphaltic base residuums by the use of heat and air or heat and other oxidizing agent such processes and products are not in any sense analogous to mine as they cause certain chemical reactions not found in my process and produce products radically different from the products produced by the present invention. It is also true that asphaltic products have heretofore been made from a strictly asphaltic base residuum by the use of heat and saturated steam, my new product however, can not -be 'made from semi- .asphaltic base residuum by the use of saturated steam for the reason that in order to distiloff-the paraflin and Vaseline hydrocarbons with saturated steam it is necessary to raise the temperature so high that cracking or decomposition results. Nor can these hydrocarbons be distilled by straight distillation with heat alonewithoutdecomposi-- tion as-the paraffin and vaseline hydrocar-- v bons will decompose at temperatures below that at which they can be removed from the I still.

sure the major portion of the paraflin and Vaseline (amorphousparafiin) hydrocarbons contained in the residuum can be removed from the still without decomposition, the temperature being however, considerably be ,low that at which the hydrocarbons would decompose. The paraffin and Vaseline hydrocarbons referred to are those saturated hydrocarbons which are non-removable by concentrated sulfur acid, (H SO it being understood that the unsaturated hydrocarof an apparatus suitable for carrying out the present invention; Fig. 2 is a detailed view of one of the branch steam pipes with which the still is equipped.

Referring now to the drawings-1 designates a supply pipe leading from any suitable source of steam supply, such as exhaust steam or low pressure steamffrom a boiler. This pipe 1 is connected to steam coil 2 of a suitable superheater 3, whereby the exhaust steam or low pressure steam is superheated. 45 designates a horizontal still having the usual fire box 5, combustion chamber 6 and stack 7. The upper part of the still is equipped with a steam dome 8 having asa-fety valve 9. superheated steam is admitted to, the still through a pipe, 10, which connects with a delivery pipe 11 lying along the bottom of the still. delivery pipe is provided'with a plurality of curved branch pipes 12 perforated along This their .lower sides as shown at 13, 13. The 1 pipe 10 is provided with a three way-cock 14 arranged so that the superheated steam may be admitted to the still, or opened to the atmosphere or entirely shut off. The supply pipe 10 is also provided with a check valve 15 in order to prevent any of the 7 residuum backing into the superheater, and

causing an explosion. The products of distillation pass from the still into a condenser 16 provided with the usual closed condenser coil 17. The products of distillation are 7 drawn off through a discharge pipe 18 to a suitable receptacle (not shown) where they may be separated and treated as-desired.

The treatment of the 'distillates, however,

"forms no part of the present invention.

Describing now the manner of carrying out such process, the still is charged with semi-asphaltic base petroleum residuum such as is obtained from mid-continentfields.

This residuum is preferably of relatively distil.

consistency has been obtained,

superheated to a temperature of from about 600 to 700 F. is admitted into the still in large quantities butat relatively low pressure. Ordinarily a pressure slightly in excess of that necessary to overcome the head of the residuum will be sulficient, it being understood however, that the superheated steam shall be introduced into the residuum in such quantities and at such pressure as to blast or thoroughly agitate thelatter. .By means of the perforated branch pipes the superheated steam is distributed throughout the residuum and intimately mixed with the latter. As the treatment proceeds the temperature of the still may be raised to as high as 700 F. depending'upon the character and gravity of the residuum used and upon the grade of product desired. The temperature, however, is at all times kept below that at which-the residuum would normally boilor The process is continued until a product of the desired melting point and care alwa s being taken to keep the temperature suciently low to avoid any danger of decomposion. This superheated steam passing through and agitating the residuum, in efiect, so varies the'vapor pressure of the residuum and of the. paraifin and Vaseline hydrocarbons that the latter are removed from the still'at temperatures considerably below that at which they would normally decompose If the process be carried out far enough the major rtion of the paraflin and Vaseline hydrocar ons contained in the original residuum can beremo'ved without decomposition or without injuring the aspgaltic-hydrocarbons remaining. It is well own to asphalt chemists that the presence of these heavy Vaseline and paraflin hydrocarbons in asphaltic'products is undesirable,

as'these hydrocarbons are non-cem'entitious,

non-ductile, non-adhesive and greasy in character and inn-addition impart these undesirable characteristics to the asphaltic hydrocarbons when mixed with the latter. Nevertheless, no artificial asphalts or asphaltic fluxes have he'retofore been made from semi-asphaltic base petroleum residuum which were sufficiently free from these deleterious. hydrocarbons or their cracked residues to obtain a product of the character in question. It is to be understood that all of the Vaseline and paraffin hydrocarbons are not necessarily removed by my process. The softer productsinaturally will not have as large a percentage of these hydrocarbons removed as will the harder grades, in which theprocess has been carried on to a further degree, but in either case, a suflicient amount of the paraflin and Vaseline hydrocarbons must-be removed to obtain a product having the qualities and desired charactertistics. I'have found however, that in any-case it is very advisable, if not necesment:

analyses of two products made by my process will clearly illustrate the foregoing state- Specific gravity at 77 F Over 1 Over 1. Melting point 110 130 F. Ductility at 77 F Over 100 cm. Over 100 cm. Penetration at 32 F 19.... 10 Penetration at 77 92...; 32 Penetration at 115 F Over 450 213 Solubility in carbon disulfid 99. 5. 99.5 Solubility in carbon tetrachlorid 99.5 99.5

For the penetration tests the well known Dowe standard machine .and method was used. For the ductility tests also the well known Dowe briquet molds were used, hav ing a cross section of one square centimeter. The briquets are pulled apart at a standard temperature at the rate of 5- centimeters per minute. These briquets are about 5 centiboth of these products have the same penetration or consistency at 77 F. as above stated the penetration of the air blown asphalt at 32 F. is more than three times that of my product. In other words, at 32 F. my productis much harder than is the air blown asphalt product. On the other hand,

the penetration of the product produced by my process. at 115 F. is aboutthree times that of the product produced by the use of air. In short, at 115 F. air blown asphalt product is still a solid while at the same temperature my product is practically a liquid. Product 13 when compared with an.

air blown asphalt having a common basis of comparison varied in a s1m1lar manner. In-

-meters in length. Product A whencomasmuch as I have compared my product with an air blownasphalt having a common basis of comparison, as for example its consistency at 77 F., such products should have all other characteristics similar, if the products are the same or similar. From the solubilit tests above given it is also apparentt at there is no material decomposition in my products produced by my new process, and further that no material amount of carbenes are formed, the presence of carbenes as is well known,indicating the presence of decomposition products. From the foregoing analysis it will also be seen'that a product made by this process will contain less than two per cent. of coke.

From the foregoing it will be seen that my process difiers radically from the process heretofore known in that in treating residuum of the character in question it produces a product radically different from any heretofore known.

A product produced by my process is particularly adapted for those casesv in which an asphaltic product'having a high degree of cementitiousness and ductility is required, as for example, in sheet asphalt pavements and the like. Products produced by my process have a ductility at normal temperatures (77 F.) ranging from 25 to over 100 times its cross section, the degree of ductility varying with the consistency of the product. The softer products have a ductility more than 50 times greater than the ductility possessed by any heretofore known asphaltic product of common consistency made from residuum of the same character.

I claim as-my invention:

1. The process of preparing asphaltic products from semi-asphaltic base petroleum residuum, which consists in' heating the residuum in a still at a gradually in-- creasing temperature not in excess of 700 degrees F., and simultaneously blasting the charge with a non-oxidizing gas heated to a temperature not-in excess of 700 degrees F so as to distil off a greater part of the parafiin and analogous hydrocarbons contained in the original residuum without material decomposition.

2. The process of preparing asphaltic products which consists in heating semi-asphaltic base petroleum residuum in a still, simultaneously blasting the mass with large quantities of superheated steam, so as to profoundly modify the residuum, removing from such residuum the greater part of the paraflin and analogous hydrocarbons contained therein without material decomposition and without injury to the asphaltic hydrocarbons of the residuum, and thereby producing a product having a marked degree of ductility and cementitiousness.

3. The process of preparing asphaltic products which consists in heating semiasphaltic base petroleum residuum in a still at a temperature not in excess of 700 degrees F., simultaneously, blasting the mass with large quantities of superheated steam,

the process being conducted at such temperature as to remove-a considerable part of the paraflin hydrocarbons contained in'the residuum without material decomposition or. njury to the asphaltic hydrocarbons of the residuum and thereby producing a product having a marked degree of ductility and cementitiousness;

4. The process of. preparing asphaltic products which consists in heating petroleum residuum in a still at a temperature not in excess of 700 degrees F., simultaneously blasting the mass with. superheated steam at relatively high temperatures but no't inexcess of 700 degrees F., andat a minimum pressure, removing-a considerable part of the paraffin hydrocarbons contained in the residuum so as to produce a product having a high degree of ductility and marked cementitiousness.

5. The process of preparing asphaltic products from asphalt bearing base petroleum residuum, which consists in heating such residuum in a still at a temperature not in excess of 700 degrees F., and simultaneously blasting the mass with large to a temperature not in excess of 7 00 degrees F., and during said heating blasting said residuum with large quantities of steam superheated to a temperature not in excess of 7 00 degrees F., and continuing said treatmen until a major portion of the saturatec hydrocarbons, e. those non-removable by concentrated sulfuric acid, have passed out of the still, and without material decomposition.

7. The process of preparing asphaltic products from petroleum residuum, which consistsin heating such residuum in a still at a temperature between 500 F. and 700 F., and simultaneously blasting the mass with large quantities of superheated steam at a temperature not in excess of 7009 F. and continuing such treatment until a major portion of the saturated hydrocarbons, i, 6;, those non-removable by concentrated sulfuric acid, has passed out of the still, and in carrying out such process and introducing such quantities of steam and mamtammg such temperatures as will avoid any substantial decomposition.

8. The process of distilling asphalt bearmg 011 by subjecting the same to the action of heat and simultaneously injecting into the mass superheated steam, the degree of heat b8111 suflic entl low and theamount of steam being sufficiently great te -produce a sohd or seml-sohd residue free from the major portion of the paraffin hydrocarbons contained in the untreated residuum and free from any material decomposition.

9. The process of preparing an asphaltic product from an asphalt bearing oil Which consists in heating such oil in a still to a temperature above 450 deg. F., blasting the oil with large quantities of superheated steam and continuing the treatment until a large portion of the saturated hydrocarbons z. 6., those non-removable by concentrated sulfuric acid, have passed out ofthe still and regulating the temperature and "quantity of superheated steam, so as to avoid the formation of more than two per cent. of coke over and above that which may have been originally contained in the untreated oil.

10. The process of preparing from an asphalt bearing oil an asphaltic product having a relatively high degreeof ductility and cementitiousness, which consists in heating said oil in a still to a temperature in excess of 450 F., blasting the heated oil 'With large quantities of highly superheated steam and continuing the-operation until a semi-solid or solid asphaltic product is produced and regulating the temperature and quantities of superheated steam so as to avoid any substantial decomposition in the product.

11. An asphaltic product made from semiasphaltic base petroleum residuum, said product being free from a greater part of the parafiin and analogous hydrocarbons contained in the residuum and free from any material decomposition, having a relatively great ductility and possessing the characteristics of a product obtained by subjecting the semi-asphaltic base petroleum residuum in a still to the action of heat and superheated steam at temperatures sufiiciently low to avoid any material decomposition, i. 6., not

' in excess of 700 Fahrenheit. 7

12. An asphaltic product made from semiasphaltic base petroleum residuum, said product being free from a greater part of the saturated hydrocarbons contained in the original residuum and free from any material decomposition, a briquet of such material which 18 one cent meter square 1n cross sectlon and 5 centimeters in length having a ductility ranging from 25 to 100 centimeters at 77 deg. F., the degree of ductility varying with the consistency of the product.

13. An asphalticflux capable of fluxing indurated natural bitumens such as graham ites and giving to the resultant compound a high degree of ductility and cementitiousness, such flux being formed from semi-asphaltic base petroleum residuum, and having the characteristics of a product obtained by subjecting such residuum to the action of heat and superheated steam zit-temperatures sufliciently low to'remove certain portions of the saturated hydrocarbons Without material decompositions, z. 6., at temperatures not in excess of 700 Fahrenheit.

14. An asphaltic product made from semiasphaltic base petroleum residuum, markedly high in its content of unsaturated hydrocarbons, '13. 6., those removable by concentrated sulfuric acid and markedly lower in its content of saturated hydrocarbons, z. 6., those non-removable by concentrated sulfuric acid, than the residuum from which it Was derived, free from material decomposition and in general possessing the characteristics of a product obtained by subjecting a semi-asphaltic base petroleum residuum to the action of heat and superheated steam at a temperature below 700 degrees Fahrenheit.

15. An asphaltic product made from petroleum residuum markedly high in its content of unsaturated hydrocarbons, i. 6., those removable by concentrated sulfuric acid and markedly lower in its content of saturated hydrocarbons, i. 6., those non-removable by LESTER KIRSGHBRAUN.

Witnesses:

F. L. BELKNAP, J. M. Low. 

